Growth of Crystalline Materials on Two-Dimensional Inert Materials

ABSTRACT

A method of growing crystalline materials on two-dimensional inert materials comprising functionalizing a surface of a two-dimensional inert material, growing a nucleation layer on the functionalized surface, and growing a crystalline material. A crystalline material grown on a two-dimensional inert material made from the process comprising functionalizing a surface of a two-dimensional inert material, growing a nucleation layer on the functionalized surface, and growing a crystalline material.

REFERENCE TO RELATED APPLICATION

This application is a non-provisional of, and claims priority to and thebenefits of, U.S. Provisional Patent Application No. 61/774,769 filed onMar. 8, 2013, and U.S. patent application Ser. No. 14/168,517 filed onJan. 30, 2014, the entirety of each is hereby incorporated by reference.

BACKGROUND

The growth of materials directly on two-dimensional inert materials(2DIM), for example graphene, is challenging due to the lack ofout-of-plane or dangling bonds on the surface to promote bonding withthe foreign atoms.

As a result, we have employed various functionalization methods tomodify the surface to promote bond formation during low temperatureatomic layer deposition of high-k dielectrics on graphene and haveresulted in pristine dielectric/graphene interfaces without altering theadvantageous graphene electronic properties. The preferred method offunctionalization is the chemisorption of an atom forming a semi-ionicbond to the 2DIM surface that preserves the structural and electricalintegrity of the 2DIM, while providing sufficient nucleation sites forsubsequent layer deposition. Fluorination, using xenon difluoride (XeF₂)gas, is one of the methods shown to functionalize the graphene surfacewith little degradation to the graphene lattice. In fact, an increase inmobility after the deposition of a thin oxide on fluorinated graphenewith 6-7% of C—F bond has been shown. Similar approaches/arguments canbe made for the whole family of 2DIMs.

High temperature growth of III-nitrides under conventional molecularbeam epitaxy (MBE) or MOCVD conditions (500-1300° C.) directly onfunctionalized graphene would result in complete desorption of thesemi-ionically bonded fluorine (or alternative) adatom and could hinderthe advantage of fluorination, thus a low temperature albeit highquality growth of a III-N nucleation layer is important.

In order to preserve the essential fluorine functional groups, atomiclayer epitaxy (ALE) is the preferred growth method as it enables growthof thin, uniform crystalline layers at low temperatures. The inherentkinetics of ALE, allow the growth of crystalline materials at greatlyreduced temperatures relative to standard epitaxial techniques such asMOCVD.

In this disclosure we report on the first ever epitaxial growth of III-Nsemiconductor layers on graphene—a key enabler to a range of wide bandgap-2D material heterojunction devices.

SUMMARY OF DISCLOSURE Description

This disclosure pertains to a method for growing crystalline materialson inert two-dimensional materials including but not limited tographene, hexagonal boron nitride, silicene, and grasene.

Using the method of invention we have been able to grow GaN epitaxiallyusing an ALE grown AN nucleation layer on graphene 2D materials. To ourknowledge this is the first report on the epitaxial growth of anymaterial directly on graphene.

We have employed various functionalization methods to modify the surfaceto promote bond formation during low temperature atomic layer depositionof high-k dielectrics on graphene and have resulted in pristinedielectric/graphene interfaces without altering the advantageousgraphene electronic properties. The preferred method offunctionalization is the chemisorption of an atom forming a semi-ionicbond to the 2DIM surface that preserves the structural and electricalintegrity of the 2DIM, while providing sufficient nucleation sites forsubsequent layer deposition.

Fluorination, using xenon difluoride (XeF₂) gas, is one of the methodsshown to functionalize the graphene surface with little degradation tothe graphene lattice. In fact, an increase in mobility after thedeposition of a thin oxide on fluorinated graphene with 6-7% of C—F bondhas been shown. Similar approaches/arguments can be made for the wholefamily of 2DIMs.

High temperature growth of III-nitrides under conventional molecularbeam epitaxy (MBE) or MOCVD conditions (500-1300° C.) directly onfunctionalized graphene would result in complete desorption of thesemi-ionically bonded fluorine (or alternative) adatom and could hinderthe advantage of fluorination, thus a low temperature albeit highquality growth of a III-N nucleation layer is important.

In order to preserve the essential fluorine functional groups, atomiclayer epitaxy (ALE) is the preferred growth method as it enables growthof thin, uniform crystalline layers at low temperatures. The inherentkinetics of ALE, allow the growth of crystalline materials at greatlyreduced temperatures relative to standard epitaxial techniques such asMOCVD.

In this disclosure, we report on the first ever epitaxial growth ofIII-N semiconductor layers on graphene—a key enabler to a range of wideband gap-2D material heterojunction devices.

The epitaxial growth can be carried out in two steps. The first step isthe 2D material surface preparation/functionalization. The surfaces ofthese films are prepared by ex-situ and/or in-situ pretreatments.Ex-situ pretreatment encompasses the treatment with various gas-phasechemistries (XeF₂), plasma (such as but not limited to N₂, H₂, O₂, NH₃,NOR) and/or wet chemicals. In-situ pretreatment is with the plasma (H₂,N₂, mixture of N₂ and H₂, and/or ammonia or other appropriate gas). Theappropriate surface pretreatment will be different depending on thenature of the crystalline material that is desired to be deposited ontop of the 2DIMs. On pretreated surface the nucleation layers are grownvia ALE. Finally, greater or equal to one monolayer crystallinematerials (such as III-V, II-VI compound semiconductors) is grown uponthe ALE film by conventional growth methods (for example MOCVD, MBE).

DESCRIPTION OF THE DRAWINGS

The following description and drawings set forth certain illustrativeimplementations of the disclosure in detail, which are indicative ofseveral exemplary ways in which the various principles of the disclosuremay be carried out. The illustrated examples, however, are notexhaustive of the many possible embodiments of the disclosure. Otherobjects, advantages and novel features of the disclosure will be setforth in the following detailed description when considered inconjunction with the drawings.

FIG. 1: Illustration of an example of process flow of crystallinematerials growth on two-dimensional inert materials.

FIG. 2: (a) Schematic showing the GaN/AlN/graphene/SiC layeredstructure, (b) as synthesized epitaxial graphene AFM image, (c) AFMimage of 1.2 nm ALE AlN/graphene, (d) AFM image of GaN/graphene, (e) SEMimage of pristine graphene, (f) SEM image of 1.2 nm ALE AlN/graphene,(g) SEM image of GaN on AlE AlN/graphene, (h) Al atoms replace F atomscreating an AlN nucleation site on graphene resulting in the proposedcrystalline alignments. The proposed lattice mismatch between AlN andgraphene is 4.5%.

FIG. 3: Illustrates Raman spectra of GaN/AlN/graphene/SiC stack when thelaser was focused within (a) SiC (black line) (b) graphene (red line)(c) GaN (blue line). Note the graphene 2D peak at 2719 cm⁻¹ for (c).

FIG. 4: XRD peaks from the GaN/AlN/graphene/SiC stack. Insets show therocking curve of GaN (0002) and (0004) reflections. Rocking curve FHWMvalues of (0002) and (0004) peaks are 544 and 461 arcsec, respectively.

FIG. 5: Illustrates room temperature photoluminescence spectra of GaN onAlN/graphene/SiC stack. The near band edge (NBE) emission is at 3.40 eV,and there is a broad yellow line at 2.27 eV due to the presence of a Gavacancy and oxygen complex point defect.

DETAILED DESCRIPTION OF THE INVENTION

This disclosure pertains to a method for growing crystalline materialson inert 2D materials including but not limited to graphene, hexagonalboron nitride, silicene, and grasene.

Using the method of invention we have been able to grow GaN epitaxiallyusing an ALE grown AN nucleation layer on graphene 2D materials. To ourknowledge this is the first report on the epitaxial growth of anymaterial directly on graphene.

The epitaxial growth can be carried out in two steps. The first step isthe 2D material surface preparation/functionalization. The surfaces ofthese films are prepared by ex-situ and/or in-situ pretreatments.Ex-situ pretreatment encompasses the treatment with various gas-phasechemistries (XeF₂), plasma (such as but not limited to N₂, H₂, O₂, NH₃,NOR) and/or wet chemicals. In-situ pretreatment is with the plasma (H₂,N₂, mixture of N₂ and H₂, and/or ammonia or other appropriate gas). Theappropriate surface pretreatment will be different depending on thenature of the crystalline material that is desired to be deposited ontop of the 2DIMs. On pretreated surface the nucleation layers are grownvia ALE. Finally, greater or equal to one monolayer crystallinematerials (such as III-V, II-VI compound semiconductors) is grown uponthe ALE film by conventional growth methods (for example MOCVD, MBE).

EXAMPLE 1

As shown in the layer structure of FIG. 2(a), crystalline materials, forexample thin AlN and GaN layers, were grown on 2DIM, for examplegraphene.

The starting pristine graphene was about 4-5 layers thick and it followsthe surface morphology of the underlying SiC, with step edges andterraces as shown in AFM and SEM images in FIG. 2(b) and (e),respectively. At optimized ALE growth conditions, AIN is depositeduniformly on graphene; AFM and SEM images of 1.2 nm AN on XeF₂functionalized graphene in FIG. 2(c) and (f) show uniform nucleation.

FIGS. 2(d) and (g) show AFM and SEM images of epitaxial GaN on grapheneusing a 11 nm ALE AN as a nucleation layer. In FIG. 2(h) we propose thatthe AIN lattice alignment along the m-plane to fluorinated graphenereplacing a semi-ionically bound F atom by an Al atom without damagingthe graphene lattice. The lattice mismatch between graphene and AIN is4.5%, which is significantly smaller than the 13% between AIN andsapphire (which is the most commonly used substrate for III-nitridegrowth). This should lead to less defects forming during heteroepitaxialgrowth of thin layers. After targeted 800 nm of MOCVD GaN growth on thethin ALE AlN nucleation layer, step edges and terraces are still clearlyvisible, as shown in FIG. 2(d), which suggests uniform two dimensional(2D) growth of GaN. The few particles seen on the surface may be due toisland nucleation.

Additionally, the SEM image in FIG. 2(g) suggests a uniform and almostpin-hole free surface morphology of the GaN on graphene over large areasthat would be required to achieve higher device yields.

To assess if the underlining graphene remains intact beneath the GaN,Raman spectra were taken on the final structure (GaN/AlN/graphene/SiC)and shown in FIG. 2. As the GaN is relatively transparent to the pumpwavelength, when the laser was focused on the underlying graphene, the2D peak at 2719 cm⁻¹ is clearly visible demonstrating that, although theGaN growth process involved several different graphene surfaceprocessing steps and elevated temperature processing, the graphene layerwas preserved. This confirms that the AlN and GaN growth occured on thegraphene surface and not on the SiC substrate. When the laser is focusedon the SiC, the graphene peak disappears. There is no clear GaN peak, asit may be buried under the SiC background Raman signal.

The crystalline quality and orientation of the GaN on graphene wasassessed using XRD. FIG. 3 shows the XRD peaks from theGaN/AlN/graphene/SiC sample. A strong intensity from SiC is clearlyvisible.

Additionally, there are a set of peaks that are indexed to first andsecond order reflections of GaN (0002). The position of the GaN peaksconfirms that the GaN on graphene has a wurtzite structure and isepitaxial in nature.

The XRD rocking curve of GaN (0002) and (0004) peaks are shown in theinsets of FIG. 3. The rocking curve full with at half maximum (FWHM) ofthe (0002) and (0004) peaks are 544 and 461 arc-sec, respectively. Thesevalues are similar to typical rocking curve values for a 5 μm thick GaNgrown on sapphire substrates which have a lattice mismatch of 16%. Thesimilarity of these values of FWHM for an order of magnitude thinner GaNfilm may indicate that better crystalline quality material on graphenecan be achieved.

A thin aluminum nitride (AlN) nucleation layer was grown onfunctionalized epitaxial graphene (EG) using atomic layer epitaxy (ALE).This thin nucleation layer enabled subsequent growth of a thick galliumnitride (GaN) film by metalorganic chemical vapor deposition (MOCVD).

The surface morphology of these GaN/AlN/graphene layers reveals smoothand uniform surface with steps and terraces, typical of the underlyingsilicon carbide substrate after EG growth. Raman measurements show agraphene 2D peak at 2719 cm⁻¹ after GaN growth, confirming preservationof the graphene after the ALE AlN and MOCVD GaN growth process. X-raydiffraction analysis reveals [0001] oriented hexagonal GaN with arocking curve full width at half maximum (FWHM) of (0002) and (0004)peaks of 544 and 641 arc-sec, respectively. The FWHM values are similarto values of the same peaks observed for GaN grown by MOCVD on sapphire.The GaN layer has a strong room temperature photoluminescence band edgeemission at 3.40 eV due to near band edge transition implies theepitaxial layer has good optical quality GaN layer on graphene.Successful demonstration of GaN growth on graphene opens up thepossibility of III-nitride/graphene heterostructure-based electronicdevices and promises improved performance.

For high-speed current switching applications, hot-electron transistors(HET) are superior to all other types of devices with cut-offfrequencies greater than 1 THz. The typical state-of-art HET base layerconsists of either a heavily doped semiconductor or metal. In HETs witha heavily doped semiconductor base, the ballistic or quasi-ballistictransportation of hot-electrons is inhibited by impurity andcarrier-carrier scattering.

Whereas for HETs with a metal base, the quantum mechanical reflection atthe interface between metal and semiconductor partially prevents ahot-electron from being transmitted to the collector region, whichlimits the device performance. Clearly it is desirable to replace thetypical base layer with a material that does not suffer from the aboveproblems.

Here, we propose replacing the base layer with graphene since it shouldovercome the limitations noted above and enable cut-off frequencies inexcess of 1 THz. Further, we demonstrate that III-V HET structures canbe epitaxially grown on a graphene base using a graphenefluorine-functionalization approach that does not appreciably disruptthe graphene lattice.

We further show, for the first time, that the resulting quality of theIII-V nitride layers is similar to that obtained by traditional growthmethods on traditional III-V nitride substrates.

Previously, Knook et al., grew GaN on oxygen plasma treated graphene,which resulted in a polycrystalline GaN layer with a rough and irregularsurface. Additionally, they explored the use of vertically-aligned ZnOnanowalls as an intermediate layer on oxygen plasma treated graphene togrow GaN-based LEDs. The oxidized graphene and complex semiconductorinterface of such an approach are certain to present significant trapcenters for carriers, and hence degrade performance of theheterojunction.

Thus, the ability to grow semiconductor quality III-nitrides directly onthe graphene with minimal interface defects is essential for suchapplications.

Although several efforts to deposit high-κ dielectrics on graphene, thesuccessful growth of high-quality III-nitride film on graphene has notbeen reported yet. Yet, there is information regarding the band line upfor this system through the work of Zhong et al., who studied theelectrical behavior of exfoliated graphene on n- and p-type GaN films.They reported that the single layer graphene adapts its Fermi leveltoward the semiconductor's Fermi level, which results in reduced barrierheights between graphene and both n- and p-type GaN.

The growth of III-nitrides directly on graphene is challenging as thereare no dangling bonds on the surface of graphene to promote bonding withforeign atoms. As a result, we have employed various functionalizationmethods to modify the graphene surface to promote bond formation andcreate pristine dielectric/graphene interfaces without altering theadvantageous graphene electronic properties.

Fluorination, using xenon difluoride (XeF₂) gas at room temperature, isone of the methods reported to functionalize the epitaxial graphenesurface for enhanced dielectric deposition, which when optimized showslittle to no degradation to the graphene lattice as measured byelectronic transport.

In fact, an increase in graphene carrier mobility after the depositionof a thin high-κ oxide on fluorinated graphene using an optimal 6-7%areal percentage of C—F bonding has been shown.

The chemisorption of a fluorine atom forming a unique semi-ionic C—Fbond rather than covalent bond to the graphene surface allows thestructural and electrical integrity of the graphene to be preserved,while providing sufficient nucleation sites for subsequent high-qualitylayer deposition. Thus, fluorination via XeF₂ is the preferredfunctionalization method employed in this work.

High temperature growth of III-nitride under conventional molecular beamepitaxy (MBE) or MOCVD conditions (500-1300° C.) directly onfunctionalized graphene can result in complete desorption of thefluorine adatom and could hinder the advantage of fluorination, thus alow temperature albeit high quality growth of a III-N nucleation layeris important.

Atomic layer epitaxy (ALE) enables growth of thin, uniform layers at lowtemperatures needed to preserve the essential fluorine functionalgroups.

The inherent kinetics of ALE allow the growth of crystalline materialsat greatly reduced temperatures relative to standard epitaxialtechniques such as MOCVD. In this work we report on the first everepitaxial growth of III-N semiconductor layers on epitaxial graphene(EG) by using XeF₂ functionalization followed by an ALE III-N bufferlayer; as is shown, this is a key enabler to a range of newheterojunction devices.

EXAMPLE 2

EG was grown on 4° 4H-SiC (16×16 mm²) samples using the Si sublimationmethod. The synthesized EG layers were characterized using atomic forcemicroscopy (AFM), LEO supra 55 scanning electron microscopy (SEM),Thermo Scientific K-Alpha x-ray photo electron spectroscopy (XPS), androom temperature Raman and photoluminescence measurements.

The Raman characterization was performed using an InVia Raman microscope(Renishaw) equipped with a 50× objective lens, a 514.5 nm diode laserexcitation, at a set power of 20 mW at the source with a spot size of 5μm.

Following initial characterization, the EG/SiC was patterned withSiN_(x) deposited by plasma-enhanced chemical vapor deposition usingstandard photolithography and liftoff techniques. The patterned EG wasfunctionalized using six, 30-second pulses of a XeF₂ plasma to formabout 6-7% of “semi-ionic” C—F bonds.

The selectively functionalized graphene was then inserted into a FijiALE reactor (Cambridge NanoTech, Inc.) heated resistively at 280° C. forthe growth AlN nucleation layer approximately 11 nm thick.

A Si(111) witness sample was used to monitor the growth rate. Afterpumping the reactor to its base vacuum of 166 mTorr, five pulses of99.999% pure trimethylaluminum (TMA, 1 Torr) (from Stream ChemicalsInc.) were introduced into the reactor to promote reaction of the TMAmolecule with fluorine sites on the EG surface, presumably creating morenucleation sites for AlN growth.

The ALE growth of AlN was carried out in an Ar ambient. Each ALE cycleconsisted of first a 60 ms TMA pulse. The TMA was added to 30 sccm flowof ultrahigh purity (UHP) Ar carrier gas via the metalorganic precursorline while 100 sccm of UHP Ar was introduced separately through theplasma source. For 30/100 sccm flow of UHP Ar, the reactor pressure wasat 166 mTorr. Unreacted TMA precursor and by-products were removed bypurging the chamber with UHP Ar for 10 sec.

A 15 s long, 150 W UHP N₂ plasma pulse was used as a nitrogen precursor.To remove unreacted nitrogen precursors and by-products, the depositionchamber was purged again with UHP Ar for 10 s.

The complete AlN growth consisted of 150 cycles, resulting in an AlNthickness of 11 nm on the Si witness sample as measured withspectroscopic ellipsometry.

An AFM operating in tapping mode was used to verify the uniformity ofthe AlN. After characterization of the ALE grown AlN/EG, the sample wastransferred into a MOCVD reactor. Unintentionally doped GaN of targetedthickness of 800 nm was grown in a heavily modified vertical impingingflow MOCVD reactor (CVD, Inc.) with a rotating susceptor.

Chemical bonding within the GaN/AlN/graphene/SiC stack (GaN/graphene)was characterized by x-ray photoelectron spectroscopy (XPS) using amonochromatic Al (Ka =1486.6 eV) source and spot size of 0.4 mm. Ramanspectra were acquired using an argon laser (514.5 nm) with 5 μm spotsize as an excitation source on the final structure. The crystallinequality was characterized using double crystal X-ray diffractometer.

Photoluminescence (PL) measurement was carried out using HeCd laser at325 nm, 1800 gr/mm double grating spectrometer, fitted with an UVsensitive photomultiplier tube.

Several initial attempts were made to grow MOCVD GaN directly onunfunctionalized EG, which always resulted in a non-uniform distributionof individual GaN crystallites instead of a continuous film. Based onprevious work, we suggest that using fluorination with XeF₂significantly increases the density of nucleation sites whichsubsequently promotes uniform, epitaxial growth.

To ensure that such functionalization survives to promote nucleation, alow temperature epitaxial growth processes is required at least at thebeginning of the heteroepitaxy process, which in this case is the ALE ofAlN. Therefore, our approach uses a fluorine functionalized EG surfaceto enable a thin ALE AlN buffer layer for subsequent thick GaN growth.

As shown in the layer structure of FIG. 2(a), thin AlN and GaN layershave been grown on both graphene and the adjacent SiN_(x) mask. Thestarting pristine graphene was about 4-5 layers thick and it follows thesurface morphology of the underlying SiC, with step edges and terracesas shown in AFM and SEM images in FIGS. 2(b) and (e), respectively.

At optimized ALE growth conditions, AlN is deposited uniformly on EG;AFM and SEM images of 1.2 nm AlN on XeF₂ functionalized EG in FIG. 2(c)and (f) show uniform nucleation. FIGS. 2(d) and (g) show AFM and SEMimages of epitaxial GaN on EG using a 11 nm ALE AlN as a nucleationlayer.

In FIG. 2(h) we show the AlN lattice alignment along m-plane tofluorinated graphene replacing a semi-ionically bound F atom by an Alatom without damaging the graphene lattice. The lattice mismatch betweengraphene and AlN is 4.5%, which is significantly smaller than the 13%between AlN and sapphire (which is the most commonly used substrate forIII-nitride growth), and leads to less defects forming duringheteroepitaxial growth of thin layers.

After targeted 800 nm of MOCVD GaN growth on the thin ALE AlN nucleationlayer, step edges and terraces are still clearly visible as shown inFIG. 2(d), which suggests uniform two dimensional (2D) growth of GaN.The few particles seen on the surface may be due to island nucleation.Additionally, the SEM image in FIG. 2(g) suggests a uniform and almostpin-hole free surface morphology of the GaN on graphene over large areasthat would be required to achieve higher device yields.

To assess if is the graphene remains underneath the GaN, Raman spectrawere taken on the final structure (GaN/AlN/graphene/SiC) and shown inFIG. 3. As the GaN is relatively transparent to the pump wavelength,when the laser was focused on the underlying graphene, the 2D peak at2719 cm⁻¹ is clearly visible implying that, although the GaN growthprocess involved several different graphene surface processing steps,the graphene layer was preserved. This confirms that the AlN and GaNgrowth was on graphene not on the SiC. When the laser is focused on theSiC, the graphene peak disappears. There is no clear GaN peak, as it maybe buried under the SiC background Raman signal.

The crystalline quality and orientation of the GaN on EG was assessedusing XRD. FIG. 4 shows the XRD peaks from the GaN/AlN/graphene/SiCsample. Strong intensity from SiC is clearly visible. Additionally,there are a set of peaks that are indexed to first and second orderreflections of GaN (0002). The position of the GaN peaks confirms thatthe GaN on graphene has a wurtzite structure and is epitaxial in nature.The XRD rocking curve of GaN (0002) and (0004) peaks are shown in theinsets of FIG. 3. The rocking curve full with at half maximum (FWHM) ofthe (0002) and (0004) peaks are 544 and 461 arcsec, respectively. Thesevalues are similar to typical rocking curve values for a 5 μm thick GaNgrown on sapphire substrates which have a lattice mismatch of 16%. Thesimilarity of these values of FWHM for an order of magnitude thinner GaNfilm may indicate that better crystalline quality material on EG can beachieved.

FIG. 5 shows room temperature PL spectra of the GaN on EG. There isclearly a near band edge (NBE) emission at 3.40 eV, and a broad yellowline at 2.27 eV. The NBE emission could result from the freeelectron-hole pair recombination in GaN, considering its low bindingenergy of about 20 meV, or band to band recombination. The yellow linemay be due to the presence of a Ga vacancy and oxygen complex pointdefect. Strong intensity of the GaN near band edge emission indicates agood optical quality of the GaN/graphene.

The two steps growth, functionalization and low temperature epitaxy, arethe keys to the successful growth of GaN on EG. The reaction of TMAmolecules with surface fluorine that is semi-ionically bonded to carbonin the top graphene layer results in a substitution of aluminum forfluorine and a creation of reaction sites for subsequent AlN growth asshown in FIG. 2(h).

XPS measurements after 1.2 nm of ALE AlN growth did not detect fluorine,which supports the claim that the functionalized fluorine simplyinitiated the ALE growth. Because of less strain, heteroepitaxial growthof GaN on ALE AlN/EG resulted in a higher crystalline quality GaNmaterial once the growth condition is optimized. Hence, the optimumproperties of both GaN and graphene can be utilized for the deviceapplications such as hot-electron transistors.

As such, GaN on epitaxial graphene/SiC was grown by MOCVD using theenabling techniques of fluorine functionalization graphene followed by alow temperature ALE of an AlN nucleation layer. The graphene 2D Ramanpeak at 2719 cm⁻¹ from GaN/AlN/graphene/SiC stack confirms the graphemefilm is preserved after the AlN and GaN subsequent growth. SEM and AFMimages show that the GaN is uniform and pinhole free. The XRD peaks showthat the GaN is epitaxial and [0001] oriented with the rocking curveFHWM of 544 and 461 arcsec for (0002) and (0004) peaks, respectively.These FWHM values are close to the typical reported values ofstate-of-the-art GaN grown heteroepitaxially on sapphire. The PLmeasurement reveals a strong room temperature band edge emission at 3.40eV. These results support a successful demonstration of electronicquality, heteroepitxial wurtizic GaN on graphene, which could be auseful heterojunction in a variety of devices.

The above examples are merely illustrative of several possibleembodiments of various aspects of the present disclosure, whereinequivalent alterations and/or modifications will occur to others skilledin the art upon reading and understanding this specification and theannexed drawings. In addition, although a particular feature of thedisclosure may have been illustrated and/or described with respect toonly one of several implementations, such feature may be combined withone or more other features of the other implementations as may bedesired and advantageous for any given or particular application. Also,to the extent that the terms “including”, “includes”, “having”, “has”,“with”, or variants thereof are used in the detailed description and/orin the claims, such terms are intended to be inclusive in a mannersimilar to the term “comprising”.

What we claim is:
 1. A method of growing epitaxial GaN or AlNcrystalline materials from two-dimensional inert materials consistingof: functionalizing a surface of a two-dimensional inert material andcreating a functionalized surface; wherein the two-dimensional inertmaterial is graphene; utilizing Atomic Layer Epitaxy; growing anucleation layer from the functionalized surface; wherein the nucleationlayer is grown via Atomic Layer Epitaxy; and growing a crystallinematerial from the nucleation layer; wherein the crystalline material isa monolayer crystalline epitaxial material; wherein the functionalizinga surface of a two-dimensional inert material further comprisespretreating the surface with ex-situ and/or in-situ pretreatment;wherein the pretreating the surface with ex-situ pretreatment comprisestreating with one selected from the group consisting of XeF₂, plasmasuch as N₂, H₂, O₂, NH₃, NO_(x), and wet chemicals; wherein thepretreating the surface with in-situ pretreatment is with a plasma;wherein the plasma is one selected from the group consisting of H₂, N₂,mixture of N₂ and H₂, and ammonia; and wherein the monolayer crystallinematerial is a III-V compound semiconductor or a II-VI compoundsemiconductor.
 2. The method of growing epitaxial GaN or AlN crystallinematerials from two-dimensional inert materials of claim 1 wherein Ramanmeasurements show a graphene 2D peak at 2719 cm⁻¹ after the galliumnitride growth and X-ray diffraction analysis reveals [0001] orientedhexagonal GaN with a rocking curve full width at half maximum (FWHM) of(0002) and (0004) peaks of 544 and 641 arc-sec, respectively.
 3. Themethod of growing epitaxial GaN or AlN crystalline materials fromtwo-dimensional inert materials of claim 1 wherein the GaN film has aroom temperature photoluminescence band edge emission at 3.40 eV due tonear band edge transition.